CN103155112A - Grinding fluid and grinding method for substrate using the grinding fluid - Google Patents

Grinding fluid and grinding method for substrate using the grinding fluid Download PDF

Info

Publication number
CN103155112A
CN103155112A CN2011800486584A CN201180048658A CN103155112A CN 103155112 A CN103155112 A CN 103155112A CN 2011800486584 A CN2011800486584 A CN 2011800486584A CN 201180048658 A CN201180048658 A CN 201180048658A CN 103155112 A CN103155112 A CN 103155112A
Authority
CN
China
Prior art keywords
acid
grinding
lapping liquid
liquid
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800486584A
Other languages
Chinese (zh)
Other versions
CN103155112B (en
Inventor
太田宗宏
田中孝明
泷泽寿夫
吉川茂
松本贵彬
吉川贵浩
筱田隆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lishennoco Co ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201610843068.5A priority Critical patent/CN106433480A/en
Publication of CN103155112A publication Critical patent/CN103155112A/en
Application granted granted Critical
Publication of CN103155112B publication Critical patent/CN103155112B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H01L21/31055—Planarisation of the insulating layers involving a dielectric removal step the removal being a chemical etching step, e.g. dry etching
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step

Abstract

A grinding fluid is provided, which contains cerium oxide particles, an organic acid A, a polymer compound B having carboxylic groups or carboxylate groups, and water. The organic acid A contains at least one group selected from the group consisting of -COOM groups, -Ph-OM groups, -SO3M groups and -PO3M2 group. The pKa of the organic acid A is less than 9. The contents of organic acid A is 0.001 mass% to 1 mass% relative to the total mass of the grinding fluid. The contents of the polymer compound B is 0.01 mass% to 0.50 mass% relative to the total mass of the grinding fluid, and the pH value of the polymer compound B is 4 or more and 7 or less.

Description

Lapping liquid and use the Ginding process of the substrate of this lapping liquid
Technical field
The present invention relates to lapping liquid and use the Ginding process of the substrate of this lapping liquid.More specifically, the present invention relates to as the planarization operation semiconductor element manufacturing technology, substrate surface, the lapping liquid that the planarization operation of interlayer dielectric, bpsg film (silicon dioxide film of the boron that adulterated, phosphorus) particularly, shallow trench isolation are used in the formation operation of (STI) etc. and the Ginding process that uses the substrate of this lapping liquid.
Background technology
In present ULSI semiconductor element manufacturing process, make the process technology of semiconductor element high density, miniaturization be studied exploitation to being used for.CMP(Chemical mechanical polishing as one of this process technology: cmp) technology, necessary technology when becoming gradually planarization, STI formation, connector and the formation of embedded metal circuit of carrying out interlayer dielectric in semiconductor element manufacturing process etc.
In the past, in semiconductor element manufacturing process, the inorganic insulating membranes such as silicon oxide film were by plasma-CVD(chemical vapor-phase growing), low pressure-CVD(chemical vapor-phase growing) etc. method form.As the chemical-mechanical grinding liquid that is used for making this inorganic insulating membrane planarization, research is that the use aerosil is lapping liquid usually.Aerosil is that lapping liquid can coordinate the pH of the slurry of particle to make by adjustment, and this particle utilizes the methods such as thermal decomposition silicon tetrachloride make germination and obtain.Yet being lapping liquid, such aerosil exist grinding rate to hang down such technical problem.
In addition, in later generation, can use STI in the element separation in integrated circuit at design standard 0.25 μ m.In STI, use the CMP technology for the unnecessary silicon oxide film of removing film forming on substrate.In this case, to stop in order making to grind in any degree of depth, can form the low stopper film of grinding rate under silicon oxide film.Stopper film can use silicon nitride film etc.In order to remove expeditiously unnecessary silicon oxide film, suppress fully its grinding afterwards simultaneously and carry out, wish that the grinding rate of silicon oxide film and stopper film is larger.Yet for former cataloid was lapping liquid, the grinding rate of silicon oxide film and stopper film was smaller, was 3 left and right, used as STI not have durable characteristic.
On the other hand, as the lapping liquid for glass surfaces such as photomask, lens, use the cerium oxide abrasive liquid that contains cerium oxide particles.Cerium oxide particles and silicon dioxide granule, that aluminium oxide particles is compared hardness is lower, is difficult for producing damage at lapped face when grinding, therefore useful to the polishing mirror ultrafinish.In addition, the silicon dioxide lapping liquids such as cerium oxide abrasive liquid and aerosil system, cataloid system are compared, and have advantages of that grinding rate is fast.
As cerium oxide abrasive liquid, put down in writing the semiconductor CMP lapping liquid that uses the high-purity cerium oxide abrasive grains in following patent documentation 1.In addition, put down in writing for the grinding rate of controlling cerium oxide abrasive liquid in following patent documentation 2, improved overall flatness and add the technology of additive.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-106994 communique
Patent documentation 2: No. 3278532 communiques of Japan's special permission
Summary of the invention
The problem that invention will solve
Yet the miniaturization that is accompanied by the design standard of circuit, STI makes progress, and requires further to improve flatness (dish that for example reduces dielectric film falls into (dishing) and measures) for above-mentioned cerium oxide abrasive liquid.In addition, the production of semiconductor device also requires further to improve precision, for example, require the residual-film thickness of dielectric film of groove density different piece poor little, superfluous amount of grinding stopper film is few.Further, the You Duda of simultaneous grinding technique, also important in the high semiconductor device of precision is produced.
The present invention is the invention of making in view of above-mentioned truth, purpose is the Ginding process that a kind of lapping liquid is provided and uses the substrate of this lapping liquid, this lapping liquid is in grinding is formed at the CMP technology that is polished film on substrate surface, the grinding rate that is polished film can be improved, and the flatness after grinding can be further improved.
The method of dealing with problems
The invention provides a kind of lapping liquid, it is to comprise cerium oxide particles, organic acid A, have the macromolecular compound B of carboxylic acid group or carboxylate group and the CMP lapping liquid of water, wherein, organic acid A have from-COOM base ,-the Ph-OM base ,-SO 3M base and-PO 3M 2(in formula, M is from H, NH to base 4, select in Na and K any, Ph represent to have also can not have substituent phenyl) at least a group selected in the group that forms, the pKa of organic acid A is less than 9, the content of organic acid A is 0.001～1 quality % with respect to the lapping liquid gross mass, the content of macromolecular compound B is 0.01～0.50 quality % with respect to the lapping liquid gross mass, and the pH of this lapping liquid is more than 4.0 below 7.0.
Lapping liquid of the present invention in grinding is formed at the CMP technology that is polished film (for example interlayer dielectric, bpsg film, STI film) on substrate surface, can improves the grinding rate that is polished film and can improve flatness after grinding.
Lapping liquid of the present invention can be used as the two liquid formula lapping liquids that are made of the 1st liquid that comprises cerium oxide particles and water and the 2nd liquid that comprises organic acid A, macromolecular compound B and water and preserves.Thus, the dispersion stabilization of cerium oxide particles can be kept better before using lapping liquid, therefore more effective grinding rate and flatness can be obtained.
In addition, lapping liquid of the present invention preferably makes above-mentioned the 1st liquid further contain dispersant.Thus, can keep better the dispersion stabilization of cerium oxide particles.
In addition, the invention provides a kind of Ginding process of substrate, the film that is polished that uses lapping liquid of the present invention to grind to form on substrate surface.Such Ginding process according to using lapping liquid of the present invention can improve the grinding rate that is polished film, and can further improve the flatness after grinding.
The invention effect
According to the present invention, the Ginding process that a kind of lapping liquid can be provided and use the substrate of this lapping liquid, this lapping liquid is in grinding is formed at the CMP technology that is polished film (for example STI film) on substrate surface, the grinding rate that is polished film can be improved, and the surface after grinding can be further improved.
Description of drawings
Fig. 1 means the constructed profile of the evaluation substrate of abrasive characteristic.
Embodiment
Below embodiments of the present invention are described in detail.
[lapping liquid]
The lapping liquid of present embodiment is the CMP lapping liquid that comprises cerium oxide particles, dispersant, organic acid A, macromolecular compound B and water.Below, each composition contained to the lapping liquid of present embodiment is described in detail.
(cerium oxide particles)
As cerium oxide particles, be not particularly limited, can use known material.Usually cerium oxide is by obtaining the cerium compound oxidations such as carbonate, nitrate, sulfate, oxalates.As the method for making cerium oxide particles, can enumerate the oxidizing process of burning till, utilize hydrogen peroxide etc. etc.
In the situation that use cerium oxide particles when grinding the silicon oxide film that forms by TEOS-CVD method etc., the crystallite diameter of cerium oxide particles (diameter of crystallite) is larger and crystallization deformation is fewer, be that crystallinity is better, more can carry out speed lapping, but have the tendency that easily produces the grinding damage on film being polished.From the viewpoint, cerium oxide particles is preferably consisted of and is had the particle of crystal boundary by the crystallite more than 2, and more preferably the crystallite diameter is the particle in 1～300nm scope.
Above-mentioned crystallite diameter can be measured by the observation of scanning electron microscope (SEM).Particularly, from by the observable image of scanning electron microscope (SEM), the long and short diameter of particle is measured, the long-pending square root of long and short diameter is designated as particle diameter.
Alkali metal in cerium oxide particles and the containing ratio of halogen, the viewpoint of using from the grinding that can be adapted at the semiconductor element manufacturing is considered, is preferably below 10ppm.
The average grain diameter of cerium oxide particles is preferably 10～500nm, more preferably 20～400nm, more preferably 50～300nm.If the average grain diameter of cerium oxide particles is more than 10nm, have the tendency that can obtain good grinding rate, if be below 500nm, have the tendency that is difficult for producing damage on film being polished.
Here, the average grain diameter of so-called cerium oxide particles, by laser diffraction formula particles distribution instrument (for example refer to, manufacturer of the Malvern company name of an article: Master Sizer Microplus, refractive index: 1.93, light source: He-Ne laser, absorption 0) the D50 value of measuring (meso-position radius of volume distributed median, accumulation median).About the mensuration of average grain diameter, use grinding fluid dilution is become sample after suitable concentration (transmitance (H) is 60～70% concentration during for example for the mensuration of He-Ne laser).In addition, cerium oxide abrasive liquid is divided in the ceria slurry that makes as described later cerium oxide particles be dispersed in water gained and additive is dissolved in the water situation that the annex solution of gained preserves, ceria slurry can be diluted to suitable concentration and measures.
The content of cerium oxide particles is considered from the viewpoint with the tendency that can obtain good grinding rate, more than being preferably 0.1 quality % in lapping liquid gross mass benchmark, more preferably more than 0.5 quality %.In addition, the content of cerium oxide particles from having the cohesion that suppresses particle and considering in the viewpoint of the tendency that is polished the difficult generation damage of film, is preferably below 20 quality %, more preferably below 5 quality %, more preferably below 1.5 quality %.
(organic acid A)
The lapping liquid of present embodiment contains organic acid and/or its salt as organic acid A.Thus, can improve grinding rate, and improve the flatness that is polished film (for example silicon oxide film) that grinds after finishing.More specifically, lap is irregular when being polished face, except shortening milling time, can also suppress because a part is produced phenomenon sagging as plate by superfluous the grinding, i.e. dish sunken (Dishing).With organic acid and/or its salt and cerium oxide particles, can obtain more expeditiously this effect by also.
Organic acid and/or its salt have from-COOM base ,-Ph-OM base (phenol-OM yl) ,-SO 3M base and-PO 3M 2(in formula, M is from H, NH to base 4, select in the group that forms of Na and K any, Ph represent to have also can not have substituent phenyl) at least a group selected in the group that forms, be preferably water miscible organic compound.
as organic acid A, for example can enumerate formic acid, acetic acid, propionic acid, butyric acid, valeric acid, cyclohexane-carboxylic acid, phenylacetic acid, benzoic acid, ortho-toluic acid, meta-toluic acid, paratolunitrile, o-methoxybenzoic acid, m-methoxybenzoic acid, P-methoxybenzoic acid, acrylic acid, methacrylic acid, butenoic acid, penetenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decylenic acid, undecenoic acid, lauroleic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, gaidic acid, heptadecenoic acid, isobutyric acid, isovaleric acid, cinnamic acid, quinaldinic acid, nicotinic acid, the 1-naphthoic acid, the 2-naphthoic acid, pyridine carboxylic acid, vinyl acetic acid, phenylacetic acid, phenoxy acetic acid, the 2-furancarboxylic acid, TGA, levulic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dioctyl phthalate, 1,11-hendecane dioctyl phthalate, 1,12-dodecane dioctyl phthalate, 1,13-tridecane dioctyl phthalate, 1,14-tetradecane dioctyl phthalate, 1,15-pentadecane dioctyl phthalate, 1,16-hexadecane dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, quinolinic acid, quininic acid, naphthoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), glycolic, lactic acid, the 3-hydracrylic acid, the 2-hydroxybutyric acid, 3-hydroxybutyrate, 4 hydroxybutyric acid, the 3-hydroxypentanoic acid, the 5-hydroxypentanoic acid, chinic acid, kynurenic acid, salicylic acid, tartaric acid, aconitic acid, ascorbic acid, acetylsalicylic acid, the acetyl malic acid, the butine dioctyl phthalate, acetyl oxygen succinic acid, acetoacetate, the 3-ketoglutaric acid, atropic acid, atrolactinic acid, anthraquinone carboxylic acids, the anthracene carboxylic acid, isocaproic acid, isocamphor three acid, methacrylate, 2-ethyl-2-hydroxybutyric acid, ethyl malonic acid, ethoxyacetic acid, oxaloacetic acid, the oxo oxalic acid, 2-Oxobutyric acid, camphoronic acid (camphoronic acid), citric acid, glyoxalic acid, glycidic acid, glyceric acid, glucaric acid, gluconic acid, crocic acid, cyclobutane-carboxylic acid, cyclohexane cyclohexanedimethanodibasic, diphenyl acetic acid, two-O-benzoyl tartaric acid, dimethyl succinic acid, the dimethoxy phthalic acid, tartronic acid, tannic acid, the thiophene carboxylic acid, tiglic acid, desoxalic acid, tetrahydroxysuccnic acid, tetramethyl-succinic acid, tetronic acid, dehydroactic acid, terebic acid, tropic acid, vanillic acid, paraconic acid, Hydroxy M Phthalic Acid, hydroxycinnamic acid, hydroxynaphthoic acid, o-hydroxy phenylacetic acid, between hydroxyl phenylacetic acid, p-hydroxyphenylaceticacid, 3-hydroxyl-3-phenylpropionic acid, pivalic acid, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyruvic acid, α-Phenylcinnamic Acid, phenyl glycidyl acid, phenylsuccinic acid, phenylacetic acid, phenyl-lactic acid, propiolic acid, sorbic acid, 2,4-muconic acid, 2-benzal propionic acid, 3-benzal propionic acid, benzal malonic acid, benzoic acid, benzenetricarboxylic acid, 1,2-phenylenediacetic Acid, benzyloxy acetic acid, the benzyloxy propionic acid, benzoyl formic acid, benzoyl acetic acid, the O-benzoyl lactic acid, the 3-benzoylamino propionic acid, gallic acid, mesoxalic acid, the oreinol dioctyl phthalate, the 2-methylcrotonic acid, α-benzylidene propionic acid, dimethyl succinic acid, methylmalonic acid, 2-Methyl Butyric Acid, the O-methoxy cinnamic acid, to methoxy cinnamic acid, dimercaptosuccinic acid, TGA, O-lactyl lactic acid, malic acid, leukonic acid, leucine, rhodizonic acid, rosolic acid, KG, L-AA, iduronic acid, galacturonic acid, glucuronic acid, pyroglutamic acid, hexamethylene tetraacetic acid, the cyaniding triacetic acid, aspartic acid, glutamic acid, N '-ethoxy-N, N, the carboxylic acids such as N '-triacetic acid and NTA,
Methanesulfonic acid, ethyl sulfonic acid, propane sulfonic acid, fourth sulfonic acid, penta sulfonic acid, own sulfonic acid, heptan sulfonic acid, hot sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, the last of the ten Heavenly stems sulfonic acid such as sulfonic acid, hendecane sulfonic acid, dodecane sulfonic acid, tridecane sulfonic acid, tetradecane sulfonic acid, pentadecane sulfonic acid, hexadecane sulfonic acid, heptadecane sulfonic acid, octadecane sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, toluenesulfonic acid, ethylenehydrinsulfonic acid, hydroxyl phenol sulfonic acid and rylnthracene sulfonin;
The phosphonic acids such as decylphosphonic acid and phenyl-phosphonic acid; Deng.Further, about above-mentioned carboxylic acid, sulfonic acid and phosphonic acids, can be also that the proton of their main chains is by the F more than 1 or 2, Cl, Br, I, OH, CN and NO 2Replace and the derivative of formation in atom or atomic group.They can use separately a kind or make up more than 2 kinds and to use.
Organic acid A(organic acid and or its salt) content count 0.001～1 quality % with lapping liquid gross mass benchmark.If the content of organic acid and/or its salt is more than 0.001 quality %, have and to improve the tendency of grinding the flatness that is polished film (for example silicon oxide film) after finishing, consider from this viewpoint, more than the preferred 0.005 quality % of the content of organic acid and/or its salt, more preferably more than 0.01 quality %.On the other hand, if content is below 1 quality %, has the tendency that the grinding rate that is polished film fully improves, also has in addition the tendency that suppresses the cerium oxide particles cohesion, consider from this viewpoint, the content of organic acid and/or its salt is preferably below 0.1 quality %, more preferably below 0.05 quality %.
The acid ionization constant pKa(pKa of organic acid A under room temperature (25 ℃) has 2 when above, is the pKa of minimum phase I 1) less than 9, but as pKa, preferably less than 8, be more preferably less than 7, further preferably less than 6, most preferably less than 5.If the pKa of organic acid A is less than 9, in lapping liquid, it becomes organic acid ion more than part and emits hydrogen ion at least, pH can be remained in desirable pH zone.
(macromolecular compound B)
The lapping liquid of present embodiment contains macromolecular compound B, and this macromolecular compound B has carboxylic acid group or carboxylate group.Here, the carboxylic acid group is-COOH represented functional group, carboxylate group is-and COOX represented functional group's (X is the cation from alkali, for example can enumerate ammonium ion, sodium ion and potassium ion).Especially, preferably comprise water soluble organic polymer with carboxylic acid group or carboxylate group and/or its salt as macromolecular compound B.Thus, can improve the flatness that is polished film (for example, silicon oxide film) that grinds after finishing.More specifically, lap is irregular when being polished face, can suppress due to a part by superfluous grind produces phenomenon sagging as plate, be that so-called dish is sunken.With water soluble organic polymer and/or its salt, organic acid and/or its salt and cerium oxide particles with carboxylic acid group or carboxylate group, can obtain more expeditiously this effect by also.
The water soluble organic polymer that has carboxylic acid group or carboxylate group as macromolecular compound B() object lesson, can enumerate:
Polycarboxylic acids and its salt such as poly-aspartate, polyglutamic acid, polylysine, polymalic acid, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt and metacetaldehyde acid;
The carboxylic acid group that acrylic acid, methacrylic acid, maleic acid etc. have carboxylic acid group's the homopolymers of monomer and this polymer is partly for the homopolymers of ammonium salt etc. etc.
In addition, can enumerate the copolymer of the derivatives such as Arrcostab of monomer with carboxylate group and carboxylic acid.As its object lesson, the part that can enumerate poly-(methyl) acrylic acid or poly-(methyl) acrylic acid carboxylic acid group is replaced to the polymer (hereinafter referred to as poly-(methyl) ammonium acrylate) of carboxylic acid ammonium's alkali etc.Here poly-(methyl) acrylic acid represents at least one party of polyacrylic acid and polymethylacrylic acid.
As macromolecular compound B, the carboxylic acid group that in above-mentioned, preferred acrylic acid, methacrylic acid, maleic acid etc. have carboxylic acid group's the homopolymers of monomer and this polymer partly is the homopolymers of ammonium salt etc., more preferably (methyl) acrylic acid homopolymers (poly-(methyl) acrylic acid) and ammonium salt thereof, further optimization polypropylene acid and ammonium salt thereof.
The content of macromolecular compound B, consider from having the viewpoint that can improve the tendency of grinding the flatness that is polished film (for example silicon oxide film) after finishing, more than counting 0.01 quality % with lapping liquid gross mass benchmark, consider from same viewpoint, more than preferred 0.02 quality %, more preferably more than 0.05 quality %.In addition, if content is below 0.50 quality %, has the tendency that the grinding rate that is polished film fully improves, consider from the viewpoint with the tendency that suppresses the cerium oxide particles cohesion in addition, the content of macromolecular compound B is counted below 0.50 quality % with lapping liquid gross mass benchmark, be preferably below 0.40 quality %, more preferably below 0.30 quality %, more preferably below 0.20 quality %.
The weight average molecular weight of macromolecular compound B is not particularly limited, but considers from the tendency with the grinding rate that can obtain fully being polished film and the viewpoint with easy inhibition cerium oxide particles cohesion, and is preferred below 100000, more preferably below 10000.Easily obtain from having the viewpoint consideration that flatness improves effect in addition, the weight average molecular weight of macromolecular compound B is preferably more than 1000.In addition, weight average molecular weight is by GPC(Gel Permeation Chromatography: gel permeation chromatography) measure, and be converted into the value of standard polyoxyethylene gained.
(water)
As water, be not particularly limited, but preferred deionized water, ion exchange water and ultra-pure water etc.The content of water can be the above-mentioned surplus that respectively contains the content of composition, is not particularly limited as long as just contain in lapping liquid.In addition, lapping liquid can further contain the solvent beyond dewatering, such as ethanol, acetone isopolarity solvent etc. as required.
(dispersant)
Can contain in the lapping liquid of present embodiment and be useful on the dispersant that disperses cerium oxide particles.As dispersant, can enumerate water soluble anion dispersant, water-soluble nonionic dispersant, water-soluble cationic dispersant and soluble amphoteric dispersant etc., wherein preferred water dissolubility anionic property dispersant.They can be used alone or make up two or more uses.In addition, also can use as the illustrated above-claimed cpd of macromolecular compound B (for example ammonium polyacrylate) as dispersant.
As the water soluble anion dispersant, preferably contain acrylic acid as macromolecule and the salt thereof of copolymer composition, more preferably this high molecular salt.As containing macromolecule and the salt thereof of acrylic acid as copolymer composition, for example can enumerate copolymer and ammonium salt and acrylamide and acrylic acid copolymer and the ammonium salt thereof of polyacrylic acid and ammonium salt thereof, acrylic acid and methacrylic acid.
As other water soluble anion dispersant, for example can enumerate dodecyltriethanolamine sulfate, ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfuric acid triethanolamine and special polyocarboxy acid type macromolecule dispersing agent.
In addition, as the water-soluble nonionic dispersant, for example can enumerate polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyglycol distearate, polyethylene glycol monooleate, polyoxyethylene alkyl amine, Crodaret, 2-hydroxyethyl methacrylate and alkyl alkanolamide.
As the water-soluble cationic dispersant, for example can enumerate PVP, coconut amine acetic acid esters and octadecylamine acetic acid esters.
As the soluble amphoteric dispersant, for example can enumerate empgen BB, octadecyl betaine, dodecyl-dimethyl amine oxide and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine.
The content of dispersant from improving the dispersiveness of cerium oxide particles, suppresses sedimentation, further reduces the viewpoint of the grinding damage that is polished film and considers, is preferably the scope of 0.001～10 quality % in lapping liquid gross mass benchmark.
The weight average molecular weight of dispersant is not particularly limited, but is preferably 100～150000, and more preferably 1000～20000.If the molecular weight of dispersant is more than 100, when grinding silicon oxide film or silicon nitride film etc. are polished film, has the tendency that easily obtains good grinding rate.If the molecular weight of dispersant is below 150000, the storage stability that has lapping liquid is difficult for the tendency of reduction.In addition, weight average molecular weight is to measure by GPC, and is converted into the value of standard polyoxyethylene gained.
[other additive]
The lapping liquid of present embodiment can use water soluble polymer as from organic acid and/or its salt and have the carboxylic acid group or the water soluble organic polymer of carboxylate group and/or the different additive of its salt.As such water soluble polymer, such as enumerating the polysaccharides such as alginic acid, pectic acid, carboxymethyl cellulose, agar, curdlan (curdlan) and pulullan polysaccharide (pullulan); The vinyl based polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein etc.
The weight average molecular weight of these water soluble polymers is preferably more than 500.In addition, weight average molecular weight is to measure by GPC, and is converted into the value of standard polyoxyethylene gained.The content of these water soluble polymers is preferably 0.01～5 quality % in lapping liquid gross mass benchmark in addition.
[modulation of lapping liquid, store method]
The lapping liquid of present embodiment for example can be by after coordinating cerium oxide particles, water and dispersant and cerium oxide particles being disperseed, and further adds organic acid A and macromolecular compound B and obtain.In addition, the lapping liquid of present embodiment can be used as and contains cerium oxide particles, dispersant, organic acid A, macromolecular compound B, water and a liquid formula lapping liquid preservation of water soluble polymer arbitrarily, also can be used as the two liquid formula lapping liquids that are made of ceria slurry (the 1st liquid) and annex solution (the 2nd liquid) preserves, this ceria slurry comprises cerium oxide particles, dispersant and water, and this annex solution comprises organic acid A, macromolecular compound B, water reaches water soluble polymer arbitrarily.
In addition, in the situation that two liquid formula lapping liquids, additive except organic acid A and macromolecular compound B can be included in ceria slurry and annex solution in any one, but never affects the dispersion stabilization aspect of cerium oxide particles, preferably is contained in annex solution.
When preserving as the two liquid formula lapping liquids that ceria slurry and annex solution are separated, by at random changing the cooperation of this two liquid, can adjust planarization characteristics and grinding rate.When using two liquid formula lapping liquids to grind, can make with the following method: carry respectively ceria slurry and annex solution by pipe arrangement separately, these pipe arrangements are merged and mix two kinds of liquid and be supplied to method on grinding pad; Before grinding with regard to the method for mixed oxidization cerium slurry and annex solution.
The lapping liquid of present embodiment and slurry, consider from the viewpoint of the cost that can suppress storage, carrying, keeping etc., can be used as the liquid medium such as water when using for example be diluted to 2 times with on use, lapping liquid takes care of with stock solution with stock solution or slurry.Above-mentioned each stock solution can dilute with liquid medium before grinding, and also stock solution and liquid medium can be supplied on grinding pad, diluted on grinding pad.
As the dilution ratio of above-mentioned stock solution, the cost inhibition of storing, carry, taking care of because multiplying power is higher etc. is just higher, and is therefore preferred more than 2 times, more preferably more than 3 times.In addition, be not particularly limited as the upper limit, but due to the contained one-tenth component of the higher stock solution of multiplying power just more (concentration is higher), stability in keeping has the tendency of reduction, therefore usually preferred below 10 times, more preferably below 7 times, further preferred below 5 times.In addition, also constituent can be divided into three kinds more than liquid, about this situation, too.
The lapping liquid of present embodiment is adjusted to desirable pH and supply in grinding.Be not particularly limited as the pH adjusting agent, such as can enumerate the acid such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, boric acid and acetic acid, and the alkali such as NaOH, ammoniacal liquor, potassium hydroxide and calcium hydroxide.In the situation that use lapping liquid in semiconductor grinding, can preferably use ammoniacal liquor, sour composition.As the pH adjusting agent, can use in advance and carry out the partly ammonium salt of the water soluble polymer of neutralization with ammonia.
In addition, be more than 4.0 below 7.0 at the pH of the lower lapping liquid of room temperature (25 ℃).Be more than 4.0 by making pH, have the tendency of the storage stability raising of lapping liquid, have the tendency of the damage generation number minimizing that is polished film, consider from same viewpoint, above-mentioned pH is preferably more than 4.5, more preferably more than 4.8.In addition, be below 7.0 by making pH, can bring into play fully the raising effect of flatness, consider from same viewpoint, above-mentioned pH is preferably below 6.5, more preferably below 6.0, more preferably below 5.5.The pH of lapping liquid can pass through pH meter (for example Model PH81 (trade name) of Yokogawa Electric Corporation's manufacturing) and measure.For example Application standard buffer solution (phthalate pH pH of buffer: 4.21(25 ℃), neutral phosphor hydrochlorate pH pH of buffer are 6.86(25 ℃)) carry out 2 point calibrations after, electrode is put into lapping liquid, be determined under 25 ℃ through the value after stable more than 2 minutes, thereby can measure the pH of lapping liquid.
Then, the lapping liquid of present embodiment described for grind the application that is polished film (Use) that forms on substrate surface.
[Ginding process]
The substrate Ginding process of present embodiment is to grind with above-mentioned lapping liquid to be polished film what substrate surface formed.More specifically, for example, be squeezed on the grinding pad of grinding plate under the state that is polished film that substrate surface forms, above-mentioned lapping liquid be supplied to be polished film and grinding pad between on one side, substrate and grinding plate are relatively moved on one side, be polished film thereby grind.
As substrate, can enumerate and form circuit element and the semiconductor substrate in line pattern stage, form substrate that the semiconductor elements such as substrate of inorganic insulating membrane make etc. on the semiconductor substrates such as semiconductor substrate that formed the circuit element stage.
As the above-mentioned film that is polished, such as inorganic insulating membranes such as the composite membrane that can enumerate silicon oxide film, silicon nitride film, silicon oxide film etc.Grind the inorganic insulating membrane that forms by the lapping liquid with present embodiment on such substrate, can eliminate the concavo-convex of inorganic insulating membrane surface, make the whole face of substrate become level and smooth face.In addition, the lapping liquid of present embodiment also can be at shallow trench isolation from middle use.
Below enumerate the situation of the semiconductor substrate that has formed inorganic insulating membrane, the Ginding process of substrate is described in further detail.
As lapping device, can use general lapping device, it possesses the grinding plate that keeps having the support of the substrates such as semiconductor substrate that are polished film and the motor that can change revolution etc. is installed and can attaches grinding pad (abrasive cloth).As lapping device, the lapping device that for example can use Ebara Corporation to make: model EPO-111, MIRRA, Reflexion etc. that AMAT makes.
As grinding pad, can use general nonwoven fabrics, polyurathamc and Porous fluororesin etc., be not particularly limited.In addition, preferably grinding pad has been implemented to be used for accumulating the such groove processing of lapping liquid.
To not restriction of grinding condition, but for semiconductor substrate is not flown out, the rotary speed of platform is preferably the low rotation below 200 rev/mins, and in order not produce damage after grinding, the pressure (machining load) that puts on semiconductor substrate is preferably below 100kPa.During grinding, by pump etc., lapping liquid is supplied to grinding pad continuously.This quantity delivered is restriction not, is to be polished liquid to cover but preferably make the total surface of grinding pad.
Semiconductor substrate after grind finishing preferably in flowing water fully after washing, will be attached to water droplet on semiconductor substrate with rotary dryer etc. and get rid of to fall behind and make its drying.
By as above using lapping liquid to grind as the inorganic insulating membrane that is polished film, can eliminate the concavo-convex of surface, obtain level and smooth face on whole of semiconductor substrate.After the shallow trench that formation is flattened, form the aluminium route on inorganic insulating membrane, after again forming inorganic insulating membrane between this circuit and on circuit, use lapping liquid to grind this inorganic insulating membrane and obtain level and smooth face.Repeat this operation by the number of times with regulation, can make the semiconductor substrate with desired number of plies.
As the inorganic insulating membrane that the lapping liquid with present embodiment grinds, for example can enumerate silicon oxide film and silicon nitride film.Silicon oxide film also can be doped with elements such as phosphorus and boron.As the manufacture method of inorganic insulating membrane, can enumerate low pressure chemical vapor deposition method, plasma CVD method.
Silicon oxide film by the low pressure chemical vapor deposition method forms, and uses single silane: SiH 4As the Si source, use oxygen: O 2As oxygen source.By making this SiH 4-O 2Be that oxidation reaction is carried out and obtains silicon oxide film at the low temperature below 400 ℃.According to circumstances, the silicon oxide film that obtains by CVD can be heat-treated at 1000 ℃ or temperature below it.In order to realize flattening surface by high temperature reflux, Doping Phosphorus in silicon oxide film: during P, preferably use SiH 4-O 2-PH 3It is reacting gas.
Plasma CVD method has advantages of to make needs the chemical reaction of high temperature to occur at low temperatures under common heat balance.In the plasma genetic method, can enumerate two kinds, capacitive coupling type and inductance coupling high type.As reacting gas, can enumerate and use SiH 4As the Si source, use N 2O is as the SiH of oxygen source 4-N 2O is gas, and is gas (TEOS-plasma CVD method) with tetraethoxysilane (TEOS) as the TEOS-O in Si source.The preferable substrate temperature is that 250～400 ℃, reaction pressure are 67～400Pa.
Silicon nitride film by the low pressure chemical vapor deposition method forms, and uses dichlorosilane: SiH 2Cl 2As the Si source, use ammonia: NH 3As nitrogenous source.By making this SiH 2Cl 2-NH 3Be that oxidation reaction occurs under the high temperature of 900 ℃ and obtains silicon nitride film.Silicon nitride film by plasma CVD method forms, and as reacting gas, can list and use SiH 4As the Si source, use NH 3SiH as nitrogenous source 4-NH 3Be gas.Substrate temperature is preferably 300～400 ℃.
The lapping liquid of present embodiment and the Ginding process of substrate be not only applicable to the inorganic insulating membrane that forms on semiconductor substrate, also applicable to manufacturing process of various semiconductor devices etc.the lapping liquid of present embodiment and the Ginding process of substrate also go for grinding the silicon oxide film that for example forms on the wiring board with regulation circuit, the inorganic insulating membrane such as glass and silicon nitride, mainly contain polysilicon, Al, Cu, Ti, TiN, W, the film of Ta and TaN etc., the optical glass such as photomask prism lens, the inorganic conductive films such as ITO, the optic integrated circuit light conversion element fiber waveguide that is consisted of by glass and crystalline material, the end face of optical fiber, the optics such as scintillator monocrystalline, the solid state laser monocrystalline, blue laser LED sapphire substrate, SiC, the semiconductor monocrystal such as GaP and GaAs, glass substrate for disc, and magnetic head etc.
Embodiment
Below, the present invention will be described by embodiment, but the present invention is not subjected to the restriction of these embodiment.
(making of cerium oxide particles)
The cerous carbonate hydrate that 40kg is commercially available is put into the aluminium oxide container made, 830 ℃, sintering in atmosphere 2 hours, thereby obtains the yellow-white powder of 20kg.When by X-ray diffraction method, this powder being carried out the identification of phases, confirming is cerium oxide.With airslide disintegrating mill, the 20kg ceria oxide powder that obtains is carried out dry type and pulverize, obtain the cerium oxide of Powdered (particle shape).When by scanning electron microscope (SEM), the Powdered cerium oxide that obtains being observed, contain the particle of crystallite size and consist of and have the particle of crystal boundary by the crystallite more than 2.At random select 50 crystallites from the SEM image that obtains, for each crystallite, when obtaining particle diameter by the long-pending square root of long and short diameter, the crystallite diameter all is included in the scope of 1～300nm.
(embodiment 1-1)
Cerium oxide particles and the 795.0g deionized water of the above-mentioned made of 200.0g are mixed, add 5g as the polyacrylic acid aqueous ammonium (weight average molecular weight: 8000,40 quality %) of dispersant, carry out the ultrasonic wave dispersion while stirring, thereby obtain cerium oxide dispersion.It is that 400kHz, jitter time are to carry out under 20 minutes that ultrasonic wave is dispersed in ultrasonic frequency.
Afterwards, 1 liter of container (highly: standing after adding the cerium oxide dispersion of 1kg 170mm), carry out classification of sedimentation.After grading time 15 hours, will release apart from the supernatant more than the degree of depth 13cm of the water surface with pump.Then, with the cerium oxide dispersion of the supernatant that obtains with the deionized water dilution so that the content of cerium oxide particles is 5 quality %, obtain ceria slurry.
For the average grain diameter (D50) of measuring the cerium oxide particles in ceria slurry, with the dilution of above-mentioned slurry, when making the mensuration for He-Ne laser, transmitance (H) is 60～70%, makes working sample.With manufacturer of the laser diffraction formula particles distribution instrument Master Sizer Microplus(Malvern company name of an article), set refractive index: 1.93, absorb: 0, measure this working sample, the D50 value is 150nm.
With the p-methyl benzenesulfonic acid-hydrate (pKa(25 ℃)=-2.8 of 0.1g as organic acid A) mix with the 800g deionized water, add 2.5g as the polyacrylic acid aqueous solution (weight average molecular weight: 4000,40 quality %), add ammoniacal liquor (25 quality %) pH is adjusted into 4.5(25 ℃) of macromolecular compound B.Further add deionized water, making total amount is 850g, makes the organic acid annex solution.
At this moment, add the above-mentioned ceria slurry of 134g, and add ammoniacal liquor (25 quality %), pH is adjusted into 5.0(25 ℃), further adding deionized water, to make total amount be 1000g, thereby made cerium oxide abrasive liquid (cerium oxide particles content: 0.67 quality %).
In addition, with the above-mentioned working sample of similarly modulating, by laser diffraction formula particles distribution instrument, the average grain diameter of the particle in lapping liquid is measured, result is that the D50 value is 150nm.
(grinding of dielectric film)
As the grinding test wafer, trade name " the graphical wafer 764 " (diameter: 300mm) that uses SEMATECH company to make.Use Fig. 1 that the evaluation method of this grinding test wafer with the abrasive characteristic that uses it described.
Fig. 1 (a) is the constructed profile that has amplified the part of grinding test wafer.Be formed with a plurality of grooves on the surface of wafer 1, being formed with thickness on the protuberance surface of wafer 1 is 150nm
Figure BDA00003019859700141
Silicon nitride film 2.The degree of depth of groove (from the surface of protuberance to the difference of height of the bottom surface of recess) is 500nm
Figure BDA00003019859700142
Below, protuberance is called active portion, recess is called groove.In addition, although do not express in Fig. 1, in wafer 1, the sectional width that has formed groove/active portion is 3 zones of 100 μ m/100 μ m, 20 μ m/80 μ m and 80 μ m/20 μ m.
Fig. 1 (b) is the constructed profile that has amplified the part of grinding test wafer.The grinding test wafer has formed silicon oxide film 3 by plasma TEOS method in active portion and groove, and making silicon oxide film 3 is 600nm apart from the thickness on active portion surface
Figure BDA00003019859700143
In grinding test, the silicon oxide film 3 of grinding test wafer is ground and carries out planarization.
Fig. 1 (c) is the constructed profile that has amplified a part of grinding the grinding test wafer after silicon oxide film 3.Silicon nitride film 2 surface in active portion finishes to grind, and will at this moment grind the needed time to be designated as milling time, and the value that will be deducted by the degree of depth 4 of groove thickness 5 gained of the silicon oxide film 3 in groove falls into amount 6 as dish.In addition, milling time is more short better, and it is the smaller the better that dish falls into amount 6.
Use lapping device (Reflexion that AMAT makes) in the grinding of such grinding test wafer.On the support of the absorption layer that has attached substrate installation use, the grinding test wafer is set.Diameter at lapping device is on the grinding plate of 600mm, attaches the resinous grinding pad of cellular polyurethane (groove shape=perforate: Rohm and Haas company makes, model IC1010).Further, make as the dielectric film (silica tunicle) that is polished film to face down, on grinding plate, the setting machining load is 210gf/cm with above-mentioned stentplacement 2(20.6kPa).
On one side the speed of above-mentioned cerium oxide abrasive liquid with 250 ml/min is dropped on above-mentioned grinding pad, Yi Bian make grinding plate and grinding test wafer separately with 130 rev/mins of work, grind thus test wafer.The milling time when silicon nitride film of the active portion in 100 μ m/100 μ m zones is exposed to the surface is as grinding the concluding time.Yet, about the evaluation of flatness, the wafer that has carried out the grinding (for example, be 100 seconds if grind the concluding time, append the time of grinding more than 20 seconds from this time) over this time 20% is carried out.This be because, from the grinding technics aspect, also have the outstanding degree of technique, be favourable, so can prove: by grind superfluously, difference easily appears in the value of assessment item, easily estimates, even grind in addition superfluously, numeral is good (characteristic is good) also.Grinding test wafer after grinding carries out drying after fully washing with pure water.
As the assessment item of flatness, 3 following projects are estimated.
The dish of the groove in project 1:100 μ m/100 μ m zone falls into (Dishing) amount: use contact pin type step instrument (model P16KLA-tencor manufacturing) to measure.
The SiN loss of the active portion in project 2:100 μ m/100 μ m zone: the interfere type determining film thickness device NANOSPEC/AFT5100(trade name of using Nanometrics company to make), measure the thickness of the silicon nitride film (SiN film) of removing by grinding.
The SiO of the groove in project 3:20 μ m/80 μ m zone and 80 μ m/20 μ m zones 2Poor (the SiO of residual-film thickness 2Density contrast): the interfere type determining film thickness device NANOSPEC/AFT5100(trade name of using Nanometrics company to make), measure the silicon oxide film (SiO in regional 2Film) residual-film thickness obtains that it is poor.
(embodiment 1-2～6-9 and comparative example 1-1～6-9)
Except the use amount with the kind of pH, the organic acid A of lapping liquid and use amount or macromolecular compound B change to shown in table 1～19, similarly make cerium oxide abrasive liquid with embodiment 1-1, and carried out the grinding of dielectric film.Show the result in same table.From table 1～19 as can be known, utilize by lapping liquid provided by the invention, grinding rate and flatness improve, and can realize the minimizing that dish falls into.
[table 1]
[table 2]
[table 3]
Figure BDA00003019859700163
[table 4]
Figure BDA00003019859700171
[table 5]
Figure BDA00003019859700172
[table 6]
[table 7]
Figure BDA00003019859700181
[table 8]
Figure BDA00003019859700182
[table 9]
Figure BDA00003019859700183
[table 10]
Figure BDA00003019859700191
[table 11]
Figure BDA00003019859700192
[table 12]
Figure BDA00003019859700193
[table 13]
Figure BDA00003019859700201
[table 14]
[table 15]
Figure BDA00003019859700203
[table 16]
Figure BDA00003019859700211
[table 17]
[table 18]
Figure BDA00003019859700213
[table 19]
Figure BDA00003019859700221
Symbol description
1: wafer; 2: silicon nitride film; 3: by the silicon oxide film of plasma TEOS method formation; 4: the degree of depth of groove; 5: the silica thickness of the groove after grinding; 6: dish falls into amount.

Claims (4)

1. lapping liquid, it is to comprise cerium oxide particles, organic acid A, have the macromolecular compound B of carboxylic acid group or carboxylate group and the CMP lapping liquid of water,
Described organic acid A have from-COOM base ,-the Ph-OM base ,-SO 3M base and-PO 3M 2At least a group of selecting in the group that base forms, in formula, M is from H, NH 4, select in the group that forms of Na and K any, Ph represents to have also and can not have substituent phenyl,
The pKa of described organic acid A is less than 9,
The content of described organic acid A is 0.001～1 quality % with respect to the lapping liquid gross mass,
The content of described macromolecular compound B is 0.01～0.50 quality % with respect to the lapping liquid gross mass, and the pH of described lapping liquid is more than 4.0 below 7.0.
2. lapping liquid according to claim 1, preserve as the two liquid formula lapping liquids that are made of the 1st liquid that comprises described cerium oxide particles and described water and the 2nd liquid that comprises described organic acid A, described macromolecular compound B and described water.
3. lapping liquid according to claim 2, described the 1st liquid further contains dispersant.
4. the Ginding process of a substrate, right to use require that in 1～3, the described lapping liquid of any one grinds the film that is polished that forms on substrate surface.
CN201180048658.4A 2010-12-24 2011-12-22 Lapping liquid and use the Ginding process of substrate of this lapping liquid Active CN103155112B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610843068.5A CN106433480A (en) 2010-12-24 2011-12-22 Polishing liquid and method for polishing substrate using the polishing liquid

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010287594 2010-12-24
JP2010-287594 2010-12-24
PCT/JP2011/079873 WO2012086781A1 (en) 2010-12-24 2011-12-22 Polishing liquid and method for polishing substrate using the polishing liquid

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201610843068.5A Division CN106433480A (en) 2010-12-24 2011-12-22 Polishing liquid and method for polishing substrate using the polishing liquid

Publications (2)

Publication Number Publication Date
CN103155112A true CN103155112A (en) 2013-06-12
CN103155112B CN103155112B (en) 2016-10-12

Family

ID=46314047

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201610843068.5A Pending CN106433480A (en) 2010-12-24 2011-12-22 Polishing liquid and method for polishing substrate using the polishing liquid
CN201180048658.4A Active CN103155112B (en) 2010-12-24 2011-12-22 Lapping liquid and use the Ginding process of substrate of this lapping liquid

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201610843068.5A Pending CN106433480A (en) 2010-12-24 2011-12-22 Polishing liquid and method for polishing substrate using the polishing liquid

Country Status (7)

Country Link
US (2) US9564337B2 (en)
JP (10) JP2012146972A (en)
KR (2) KR101389235B1 (en)
CN (2) CN106433480A (en)
SG (1) SG190765A1 (en)
TW (2) TW201350567A (en)
WO (1) WO2012086781A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105934487A (en) * 2014-01-31 2016-09-07 巴斯夫欧洲公司 Chemical mechanical polishing (CMP) composition comprising poly(aminoacid)
CN106867411A (en) * 2015-10-15 2017-06-20 三星电子株式会社 For the paste compound, its preparation method, polishing method, the method for manufacture semiconductor devices and the polissoir that chemically-mechanicapolish polish
CN107429120A (en) * 2015-03-05 2017-12-01 嘉柏微电子材料股份公司 Include the polishing composition of cation type polymer additive
CN107532066A (en) * 2015-05-08 2018-01-02 信越化学工业株式会社 The Ginding process of synthetic quartz glass substrate grinding agent and synthetic quartz glass substrate
CN110998800A (en) * 2017-08-14 2020-04-10 日立化成株式会社 Polishing liquid, polishing liquid set and polishing method

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140011362A1 (en) * 2012-07-06 2014-01-09 Basf Se Chemical mechanical polishing (cmp) composition comprising a non-ionic surfactant and an aromatic compound comprising at least one acid group
JP6015259B2 (en) * 2012-09-06 2016-10-26 旭硝子株式会社 Manufacturing method of glass substrate for information recording medium and manufacturing method of magnetic disk
JP2016522855A (en) * 2013-05-15 2016-08-04 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Chemical mechanical polishing composition comprising one or more polymers selected from the group consisting of N-vinyl homopolymers and N-vinyl copolymers
JP2016524326A (en) * 2013-05-15 2016-08-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Chemical mechanical polishing composition comprising N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylenediamine or methanesulfonic acid
JP6611485B2 (en) 2014-11-07 2019-11-27 株式会社フジミインコーポレーテッド Polishing method and polishing composition
US10946494B2 (en) * 2015-03-10 2021-03-16 Showa Denko Materials Co., Ltd. Polishing agent, stock solution for polishing agent, and polishing method
JP2017011162A (en) * 2015-06-24 2017-01-12 日立化成株式会社 Method for producing polishing liquid, polishing liquid, and polishing method
JP6551136B2 (en) * 2015-10-14 2019-07-31 日立化成株式会社 Polishing solution for CMP and polishing method
JP6708951B2 (en) * 2016-03-28 2020-06-10 日立化成株式会社 Polishing liquid and polishing method
KR102475282B1 (en) 2017-03-29 2022-12-07 삼성전자주식회사 Slurry composition for chemical mechanical polishing
JP7249725B2 (en) * 2017-08-31 2023-03-31 アドバンスト ナノ プロダクツ カンパニー リミテッド Surface treated cerium oxide powder and polishing composition
JP7220522B2 (en) * 2018-05-24 2023-02-10 株式会社バイコウスキージャパン Abrasive grains, manufacturing method thereof, polishing slurry containing the same, and polishing method using the same
US20230417935A1 (en) * 2022-06-22 2023-12-28 Ecole Polytechnique Federale De Lausanne (Epfl) High-Resolution Scintillation Detector for Two-Dimensional Reconstruction

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1453328A (en) * 2002-04-22 2003-11-05 Jsr株式会社 Aqueous dispersion body for chemical mechanical grinding
CN1572424A (en) * 2003-05-21 2005-02-02 Jsr株式会社 Chemical mechanical polishing method for sti
CN101333418A (en) * 2004-09-28 2008-12-31 日立化成工业株式会社 Cmp polishing compound and method for polishing substrate
CN101374922A (en) * 2006-01-25 2009-02-25 Lg化学株式会社 CMP slurry and method for polishing semiconductor wafer using the same
CN101432854A (en) * 2006-04-24 2009-05-13 日立化成工业株式会社 Polishing liquid for CMP and method of polishing
JP2009231795A (en) * 2008-02-27 2009-10-08 Hitachi Chem Co Ltd Polishing solution
CN101689494A (en) * 2007-07-05 2010-03-31 日立化成工业株式会社 Polishing liquid for metal film and polishing method
JP2010161201A (en) * 2009-01-08 2010-07-22 Jsr Corp Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method using the same, and method of manufacturing chemical mechanical polishing aqueous dispersion

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3278532B2 (en) 1994-07-08 2002-04-30 株式会社東芝 Method for manufacturing semiconductor device
JPH10106994A (en) 1997-01-28 1998-04-24 Hitachi Chem Co Ltd Cerium oxide abrasive agent and polishing method of substrate
TW501197B (en) * 1999-08-17 2002-09-01 Hitachi Chemical Co Ltd Polishing compound for chemical mechanical polishing and method for polishing substrate
US6740589B2 (en) * 2000-11-30 2004-05-25 Showa Denko Kabushiki Kaisha Composition for polishing semiconductor wafer, semiconductor circuit wafer, and method for producing the same
US20020068454A1 (en) * 2000-12-01 2002-06-06 Applied Materials, Inc. Method and composition for the removal of residual materials during substrate planarization
TW200300168A (en) * 2001-10-31 2003-05-16 Hitachi Chemical Co Ltd Polishing fluid and polishing method
US7005382B2 (en) * 2002-10-31 2006-02-28 Jsr Corporation Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing process, production process of semiconductor device and material for preparing an aqueous dispersion for chemical mechanical polishing
US6953532B2 (en) * 2003-03-06 2005-10-11 Cabot Microelectronics Corporation Method of polishing a lanthanide substrate
JP4637464B2 (en) * 2003-07-01 2011-02-23 Ｊｓｒ株式会社 Aqueous dispersion for chemical mechanical polishing
US20050022456A1 (en) * 2003-07-30 2005-02-03 Babu S. V. Polishing slurry and method for chemical-mechanical polishing of copper
DE10360464A1 (en) * 2003-12-22 2005-07-14 Wacker-Chemie Gmbh Dispersion containing at least 2 types of particles
CN1667026B (en) * 2004-03-12 2011-11-30 K.C.科技股份有限公司 Polishing slurry, method of producing same, and method of polishing substrate
TWI283008B (en) * 2004-05-11 2007-06-21 K C Tech Co Ltd Slurry for CMP and method of producing the same
US7303993B2 (en) * 2004-07-01 2007-12-04 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing compositions and methods relating thereto
US20070218811A1 (en) * 2004-09-27 2007-09-20 Hitachi Chemical Co., Ltd. Cmp polishing slurry and method of polishing substrate
US7086935B2 (en) * 2004-11-24 2006-08-08 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Cellulose-containing polishing compositions and methods relating thereto
WO2006078074A2 (en) * 2005-01-24 2006-07-27 Showa Denko K.K. Polishing composition and polishing method
KR101275964B1 (en) * 2005-02-23 2013-06-14 제이에스알 가부시끼가이샤 Chemical mechanical polishing method
JP5133874B2 (en) * 2005-04-28 2013-01-30 テクノ セミケム シーオー．， エルティーディー． Chemical mechanical polishing composition with automatic polishing stop function for planarization of high step oxide film
JP2006339594A (en) 2005-06-06 2006-12-14 Seimi Chem Co Ltd Abrasive agent for semiconductor
CN101039876B (en) * 2005-10-14 2011-07-27 Lg化学株式会社 Method for preparing of cerium oxide powder for chemical mechanical polishing and method for preparing of chemical mechanical polishing slurry using the same
JP2007214155A (en) * 2006-02-07 2007-08-23 Fujifilm Corp Polishing fluid for barrier, and chemical mechanical polishing method
JP5080012B2 (en) 2006-02-24 2012-11-21 富士フイルム株式会社 Polishing liquid for metal
SG136886A1 (en) * 2006-04-28 2007-11-29 Asahi Glass Co Ltd Method for producing glass substrate for magnetic disk, and magnetic disk
US7297633B1 (en) * 2006-06-05 2007-11-20 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Compositions for chemical mechanical polishing silica and silicon nitride having improved endpoint detection
JP2008181955A (en) * 2007-01-23 2008-08-07 Fujifilm Corp Polishing liquid for metal and polishing method using the same
WO2008095078A1 (en) * 2007-01-31 2008-08-07 Advanced Technology Materials, Inc. Stabilization of polymer-silica dispersions for chemical mechanical polishing slurry applications
EP2437285A2 (en) * 2007-03-26 2012-04-04 JSR Corporation Chemical mechanical polishing method for semiconductor device using an aqueous dispersion
JP5121273B2 (en) * 2007-03-29 2013-01-16 富士フイルム株式会社 Polishing liquid for metal and polishing method
KR101396853B1 (en) * 2007-07-06 2014-05-20 삼성전자주식회사 Slurry Composition for Polishing Silicon Nitride, Method of Polishing a Silicon Nitride Layer Using the Slurry Composition and Method of Manufacturing a Semiconductor Device Using the Slurry Composition
JP5178121B2 (en) * 2007-09-28 2013-04-10 富士フイルム株式会社 Polishing liquid and polishing method
KR101562416B1 (en) * 2008-02-06 2015-10-21 제이에스알 가부시끼가이샤 Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method
KR101256551B1 (en) * 2008-03-06 2013-04-19 주식회사 엘지화학 Cmp slurry and polishing method using the same
JP2009278061A (en) 2008-04-16 2009-11-26 Hitachi Chem Co Ltd Polishing solution for cmp and polishing method
JP5319968B2 (en) 2008-06-18 2013-10-16 株式会社Ａｄｅｋａ Polishing composition for CMP
CN103342986B (en) * 2008-12-11 2015-01-07 日立化成株式会社 Polishing solution for CMP and polishing method using same
WO2010143579A1 (en) * 2009-06-09 2010-12-16 日立化成工業株式会社 Abrasive slurry, abrasive set, and method for grinding substrate
WO2011049318A2 (en) * 2009-10-13 2011-04-28 주식회사 엘지화학 Slurry composition for cmp, and polishing method
CN102666771A (en) * 2009-12-31 2012-09-12 第一毛织株式会社 Cmp slurry compositions and polishing method using the same
US8435896B2 (en) * 2011-03-03 2013-05-07 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Stable, concentratable chemical mechanical polishing composition and methods relating thereto
SG11201502768UA (en) * 2012-11-02 2015-05-28 Fujimi Inc Polishing composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1453328A (en) * 2002-04-22 2003-11-05 Jsr株式会社 Aqueous dispersion body for chemical mechanical grinding
CN1572424A (en) * 2003-05-21 2005-02-02 Jsr株式会社 Chemical mechanical polishing method for sti
CN101333418A (en) * 2004-09-28 2008-12-31 日立化成工业株式会社 Cmp polishing compound and method for polishing substrate
CN101374922A (en) * 2006-01-25 2009-02-25 Lg化学株式会社 CMP slurry and method for polishing semiconductor wafer using the same
CN101432854A (en) * 2006-04-24 2009-05-13 日立化成工业株式会社 Polishing liquid for CMP and method of polishing
CN101689494A (en) * 2007-07-05 2010-03-31 日立化成工业株式会社 Polishing liquid for metal film and polishing method
JP2009231795A (en) * 2008-02-27 2009-10-08 Hitachi Chem Co Ltd Polishing solution
JP2010161201A (en) * 2009-01-08 2010-07-22 Jsr Corp Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method using the same, and method of manufacturing chemical mechanical polishing aqueous dispersion

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105934487A (en) * 2014-01-31 2016-09-07 巴斯夫欧洲公司 Chemical mechanical polishing (CMP) composition comprising poly(aminoacid)
CN105934487B (en) * 2014-01-31 2018-10-26 巴斯夫欧洲公司 Include chemically mechanical polishing (CMP) composition of polyaminoacid
CN107429120A (en) * 2015-03-05 2017-12-01 嘉柏微电子材料股份公司 Include the polishing composition of cation type polymer additive
CN107429120B (en) * 2015-03-05 2019-10-01 嘉柏微电子材料股份公司 Polishing composition comprising cation type polymer additive
CN107532066A (en) * 2015-05-08 2018-01-02 信越化学工业株式会社 The Ginding process of synthetic quartz glass substrate grinding agent and synthetic quartz glass substrate
CN107532066B (en) * 2015-05-08 2020-06-02 信越化学工业株式会社 Polishing agent for synthetic quartz glass substrate and method for polishing synthetic quartz glass substrate
US10683437B2 (en) 2015-05-08 2020-06-16 Shin-Etsu Chemical Co., Ltd. Polishing agent for synthetic quartz glass substrate and method for polishing synthetic quartz glass substrate
CN106867411A (en) * 2015-10-15 2017-06-20 三星电子株式会社 For the paste compound, its preparation method, polishing method, the method for manufacture semiconductor devices and the polissoir that chemically-mechanicapolish polish
CN110998800A (en) * 2017-08-14 2020-04-10 日立化成株式会社 Polishing liquid, polishing liquid set and polishing method
CN110998800B (en) * 2017-08-14 2023-09-22 株式会社力森诺科 Polishing liquid, polishing liquid set and polishing method

Also Published As

Publication number Publication date
JP2013149987A (en) 2013-08-01
JP2012146973A (en) 2012-08-02
JP2012146970A (en) 2012-08-02
TWI437087B (en) 2014-05-11
JP2016183346A (en) 2016-10-20
JP6269733B2 (en) 2018-01-31
JP2012146974A (en) 2012-08-02
JP2012146976A (en) 2012-08-02
US20170133237A1 (en) 2017-05-11
SG190765A1 (en) 2013-07-31
JP2013149988A (en) 2013-08-01
TW201350567A (en) 2013-12-16
JP2012146975A (en) 2012-08-02
CN103155112B (en) 2016-10-12
KR101886464B1 (en) 2018-08-07
JP5333571B2 (en) 2013-11-06
TW201229222A (en) 2012-07-16
US20130260558A1 (en) 2013-10-03
JP2012146971A (en) 2012-08-02
KR101389235B1 (en) 2014-04-24
KR20140039143A (en) 2014-04-01
JP5510574B2 (en) 2014-06-04
WO2012086781A1 (en) 2012-06-28
KR20140041388A (en) 2014-04-04
JP5510575B2 (en) 2014-06-04
CN106433480A (en) 2017-02-22
US9564337B2 (en) 2017-02-07
JP2012146972A (en) 2012-08-02

Similar Documents

Publication Publication Date Title
CN103155112A (en) Grinding fluid and grinding method for substrate using the grinding fluid
JP4729834B2 (en) CMP abrasive, substrate polishing method and semiconductor device manufacturing method using the same, and additive for CMP abrasive
JP5655879B2 (en) CMP polishing agent and substrate polishing method
TWI780194B (en) Grinding liquid, grinding liquid set and grinding method
JP2010095650A (en) Abrasives composition and method for polishing substrates using the same
JP2012186339A (en) Polishing liquid and polishing method of substrate using the same
JP2015008212A (en) Polishing liquid and substrate polishing method using the same
JP2017178986A (en) Polishing liquid and polishing method
JP2006179678A (en) Cmp abrasive for semiconductor insulating film and method for polishing substrate
JP2017075226A (en) Method for producing polishing liquid, polishing liquid and polishing method
JP2014027146A (en) Polishing solution and substrate polishing method using polishing solution
JP2015137350A (en) Polishing liquid and polishing method using the same
JP6620590B2 (en) Polishing liquid and polishing method
JP2017011162A (en) Method for producing polishing liquid, polishing liquid, and polishing method
JP2015137290A (en) Manufacturing method of polishing liquid and polishing liquid, and polishing method
TW201829678A (en) Cerium oxide abrasive grain
JP2006041034A (en) Cmp abrasive and polishing method of substrate
JP2017152577A (en) Polishing liquid and polishing method
JP2015023122A (en) Polishing liquid and production method therefor, and polishing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: Lishennoco Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: HITACHI CHEMICAL Co.,Ltd.

CP01 Change in the name or title of a patent holder